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Baldur Föhlisch Bernhard Czauderna 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):167-171
Abstract 3-Thietanone (3a) reacts rapidly with methanolic sodium hydrogen sulfide to form a mixture of products wherein 2,4-dimethylthiophene-3-thiol (9), the corresponding disulfide (10) and 3,6-dimethyl-7-oxa-2,5-dithiabicyclc [2.2.1]-heptane (7) could be detected. These products are explained to be derived from the unstable 1-mercapto-2-propanone (5) formed by reductive cleavage of the thietanone ring. The cleavage is postulated to occur by attack of hydrogensulfide ion at the ring sulfur. 3-Thietanone can be synthesized from 3-thietanol by oxidation with dimethyl sulfoxide/benzoic acid anhydride. 3-Thietanon (3a) reagiert rasch mit methanolischem Natriumhydrogensulfid zu einem Produktgemisch, in dem 2,4-Dimethylthiophen-3-thiol (9), das entsprechende Disulfid (10) und 3,6-Dimethyl-7-oxa-2,5-dithiabicyclo [2.2.1]-heptan (7) nachgewiesen werden konnten. Diese Produkte lassen sich aus dem instabilen 1-Mercapto-2-propanon (5) ableiten, welches durch reduktive Spaltung des Thietanon-Ringes gebildet wird. Für die Spaltung wird ein Angriff des Hydrogensulfidions am Ringschwefel postuliert. 3-Thietanon kann aus 3-Thietanol durch Oxidation mit Dimethyl-sulfoxid/Benzoesäureanhydrid synthetisiert werden. 相似文献
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Kai‐lu Yu Chang‐jun Liu Yue‐ping Zhang Fei He Xin‐li Zhu Baldur Eliasson 《Plasma Chemistry and Plasma Processing》2004,24(3):393-403
PdO/Al2O3 catalysts prepared by glow discharge plasma treatment followed by thermal calcination show a much higher dispersion and a better catalytic activity for methane combustion at relatively low temperatures. The dispersion of palladium active species by such plasma prepared catalysts is 29.7%, 5.4 times higher than that of conventional catalysts. XPS analysis indicates that a surface enrichment of Pd active species (PdO) has been achieved after plasma treatment. The surface atomic composition of PdO of plasma prepared catalysts reaches 10.5%. XRD characterization also confirms a wellcrystallized PdO phase present on the plasma prepared catalyst. The lightoff temperature of the plasma prepared catalyst is 370°C, 50°C lower than that obtained from the conventional catalyst. 相似文献
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Schroeter Baldur Yonkova Velislava P. Goslinska Monika Orth Maike Pietsch Swantje Gurikov Pavel Smirnova Irina Heinrich Stefan 《Cellulose (London, England)》2021,28(12):7795-7812
Cellulose - Aim of this work is to apply protective and homogeneous shellac coating layers on the surface of hydrophilic open-pore cellulose aerogel particles with low... 相似文献
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Stulgies B Prinz P Magull J Rauch K Meindl K Rühl S de Meijere A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):308-320
Palladium-catalyzed sixfold coupling of hexabromobenzene (20) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73 % and 16 to 41 % yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75 %). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24 % yield). The sixfold coupling of the less sterically encumbered 2,3,6,7,10,11-hexabromotriphenylene (24) gave the desired hexakis(3,3-dimethyl-1-butenyl)triphenylene (25) in 93 % yield. The first successful cross-coupling reaction of octabromonaphthalene (26) gave octakis-(3,3-dimethyl-1-butenyl)naphthalene (27) in 21 % yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1 a and 1 i, making them nicely cup-shaped molecules, or alternatingly above and below the central plane as in 1 h and 23. In 27, the four arms at C-1,4,6,7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1 a yielded 89 % of hexakis(tert-butylethyl)benzene (23). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1-ethynyladamantane (3 b, 62 % yield), 1-ethynyl-1-methylcyclohexane (3 c, 85 %) and 3,3-dimethylpentyne (3 e, 65 %). 1-(Trimethylsilyl)ethynylcyclopropane (7) was used to prepare 1-ethynyl-1-methylcyclopropane (3 d) (two steps, 64 % overall yield). The functionally substituted alkynes 3 f-h were synthesized in multistep sequences starting from the propargyl chloride 11, which was prepared in high yields from the dimethylpropargyl alcohol 10 (94 %). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42-97 %), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27-96 % yield) or pinacolborane (26-69 % yield). 相似文献
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Baldur Föhlisch Robert Flogaus Jutta Oexle Angelika Schädel 《Tetrahedron letters》1984,25(17):1773-1776
1,1-Dichloro- and 1,3-dichloro-2-alkanones react with 2-methylfuran in the presence of lithium perchlorate/triethylamine to form 2-chloro-1-methyl-8-oxabicyclo [3.2.1]oct-6-ene-3-ones predominantly. 相似文献
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Eccles W Jasinski M Kaszynski P Zienkiewicz K Stulgies B Jankowiak A 《The Journal of organic chemistry》2008,73(15):5732-5744
Reactions of dibromocyclopropane 2a, containing two spiro-fused 1,3-dioxane rings, with MeLi gave only the methylation products 8 and 9 even at elevated temperatures. In contrast, the cyclohexane analogue 2b treated with MeLi underwent a smooth rearrangement to bicyclo[1.1.0]butane 11b at -78, -10, or +35 degrees C. Treatment of 2a with PhLi gave the alpha-Ph anion 13 as the only product, which underwent smooth methylation with MeI to give 14. Under the same conditions, 2b with PhLi gave bicyclo[1.1.0]butane 11b accompanied by bromophenyl derivative 8b. Treatment of either dibromide with t-BuLi gave a mixture of products including debrominated cyclopropanes 12. Experimental results were augmented with DFT calculations for salts 23 and MP2//DFT-level calculations for carbenes 22. They demonstrated a higher stability of the dioxane alpha-bromo anion with respect to alpha-elimination by 4.8 kcal/mol and also a lower tendency of the carbene 22a to undergo rearrangement by 4.0 kcal/mol than the cyclohexane analogues. These differences have been attributed to the inductive effect of the four oxygen atoms, which results in lower LUMO energy, the higher positive charge at the carbenic center, and the overall more electrophilic character of carbene 22a as compared to the cyclohexane derivative 22b. The rearrangement of carbenes 22 to the corresponding allenes 1, the thermodynamic products, requires a higher activation energy DeltaG(double dagger)(298) by 4.2 kcal/mol for dioxane and 6.4 kcal/mol for cyclohexane derivatives than for the formation of the bicyclo[1.1.0]butanes 11. The DeltaG(double dagger)(298) for intramolecular insertions to the CH bond is low and calculated as 6.0 kcal/mol for dioxane 22a and 2.0 kcal/mol for the formation of cyclohexane 22b. 相似文献
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[reaction: see text] Olefination of aliphatic dithioacetals with Grignard reagents is catalyzed by Ni(acac)(2) in the presence of an appropriate trialkylphosphine ligand. 相似文献